CN109534279B - Preparation method of nanowire array device - Google Patents
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- CN109534279B CN109534279B CN201811411998.9A CN201811411998A CN109534279B CN 109534279 B CN109534279 B CN 109534279B CN 201811411998 A CN201811411998 A CN 201811411998A CN 109534279 B CN109534279 B CN 109534279B
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Abstract
The invention relates to a nanowire arrayMethod for fabricating column device by fabricating Al on substrate on which nanowire is grownxGa1‑xAs thin film As sacrificial layer, nanowire grown on AlxGa1‑xAnd (3) spin-coating a PMMA material dissolved in an acetone solution on the surface of the nanowire sample to complete the fixation of PMMA to the nanowire. Putting the nanowire sample fixed by PMMA into HF acid corrosive liquid, and utilizing HF acid to carry out Al treatmentxGa1‑xAs has corrosion effect, and HF has no corrosion effect on GaAs, InAs or PMMA, so that Al on the surface of the substratexGa1‑xAs is corroded, the GaAs nanowire and PMMA material are not reacted with HF acid and are completely reserved, and the transferable GaAs or InAs nanowire array is obtained. And then, preparing a p-type metal electrode on the upper surface of the transferable nanowire array material, preparing an n-type metal electrode on the lower surface of the transferable nanowire array material, putting a sample into an acetone or toluene solution after the electrode is prepared, soaking to remove PMMA, cleaning and naturally drying to obtain the GaAs or InAs nanowire array device, and solving the problem of difficult process in the prior art for obtaining the nanowire array device.
Description
Technical Field
The invention belongs to the field of new materials and novel nano optoelectronic devices, and particularly relates to a preparation method of a nanowire array device in the field of nano optoelectronic materials and devices.
Background
The nanometer material is a hot point of the world research at present, and is widely applied to the aspect of nanometer optoelectronic devices due to the structural particularity of the nanometer material. But because of the unique electrical and optical characteristics, the material can be used for preparing devices such as solar cells, optical switches, nano power generation, field effect transistors, light emitting diodes, nano lasers, photoelectric detectors and the like, and is rapidly developed in the fields of nano electronics and photoelectrons. Since the introduction of the ordered array structure membrane cell module in 2002, research on the structure of the ordered array membrane cell module has been attracting attention. The catalyst is loaded outside the electronic conductor, and the proton conductor is vertically loaded on the surface of the membrane structure, so that the use efficiency of the catalyst is greatly improved. The appearance of the nano array material further improves the performance of the supercapacitor with excellent performance originally, the use of the nano array material on the positive electrode and the negative electrode of the supercapacitor not only provides a quick channel for the diffusion of ions and the transmission of charges, but also increases the attachment area of the charges due to the high specific surface area of the nano array material, thereby improving the capacitance performance of the material. The preparation of a single nanowire device is extremely difficult, and the preparation method of the single nanowire device has extremely strict requirements on the process, so that the development of the nanowire device in the fields of nano electronics and photoelectrons is hindered.
The traditional photoelectric device needs to prepare n-type and p-type electrodes to realize current injection of the device, the nanowire photoelectric device also needs the n-type and p-type electrodes, but the electrode preparation of a single nanowire device is extremely difficult, the optical power of the prepared device is low and cannot meet the application requirement, how to obtain the nanowire array by adopting a simple method is a basic condition for realizing the preparation of the nanowire array device, the difficulty in preparing the electrode of the nanowire device can be reduced by obtaining the transferable nanowire array, and the realization of the nanowire array device with higher power becomes possible.
At present, the preparation process of a single nanowire device is still complex, a probe is required to be utilized, an electrode is prepared under the condition of a microscope, and the yield of the single nanowire device still has a challenge. How to reduce the difficulty of the preparation process of the nanowire device is the problem which is mainly solved for realizing the nanowire device. The realization of a single nanowire device is difficult, and therefore, starting from the nanowire material, the realization of the nanowire array material capable of being migrated can reduce the difficulty of the preparation of the nanowire device. According to the difficulty in preparing the single nanowire device, the invention provides a method for preparing a transferable nanowire array material, which is a method for realizing the nanowire array device by using the transferable nanowire array material, and further reduces the difficulty in preparing the single nanowire device.
Disclosure of Invention
The invention provides a preparation method of a nanowire array device, which comprises the following steps of firstly obtaining a mobile nanowire array material: 1. treating the substrate before growing the nanowire material, and epitaxially growing Al with the thickness of 30 nm-50 nm on the surface of the substratexGa1-xAs thin film material, AlxGa1-xThe component of Al in As is more than or equal to 0.6 and less than or equal to 1, and then Al is prepared by utilizing the surfacexGa1-xGrowing a nanowire material on the substrate of the As thin film material; 2. spin-coating PMMA on the surface of a sample with the grown nanowire material for curing, placing the sample into HF acid corrosive liquid after the PMMA material is cured, and utilizing HF acid to carry out Al etchingxGa1-xAs thin film material has corrosion effect, HF acid has no corrosion effect on GaAs and InAs material, and Al on the surface of substrate can be removedxGa1-xAs thin film material is used As sacrificial layer and is corroded away, GaAs, InAs nanowire material and solidified PMMA material are not reacted with HF acid and are completely reserved, and nanowire array material solidified by PMMA material among nanowires is obtained. The method comprises the steps of preparing a nanowire array device by using a nanowire array material fixed by a PMMA material, preparing a p-type Ti/Au alloy metal electrode on the upper surface of the nanowire array material, preparing an n-type Ni/Au alloy metal electrode on the lower surface of the nanowire array material, preparing the n-type and p-type electrodes by adopting a magnetron sputtering technology, soaking prepared samples in an acetone or toluene solution for 30-60 minutes after the preparation of the n-type and p-type electrodes is completed, sequentially cleaning the soaked samples by using alcohol and deionized water, and finally naturally drying the samples to obtain the nanowire array device.
In order to realize the purpose, the adopted technical scheme is as follows:
a method for preparing a nanowire array device comprises the steps of firstly obtaining a nanowire array material fixed by a PMMA material, and then preparing the nanowire array device by using the obtained nanowire array material fixed by the PMMA material.
The preparation method of the nanowire array device comprises the following concrete implementation steps:
the method comprises the following steps: cleaning a substrate, namely cleaning the GaAs substrate for growing the GaAs or InAs nanowire by using acetone, absolute ethyl alcohol and deionized water in sequence and drying by using nitrogen;
step two: mixing AlxGa1-xPreparing an As film on the cleaned GaAs substrate;
step three: growing a nanowire material on the substrate processed in the step two;
step four: dropping the solution dissolved with the PMMA material in the acetone solution on the surface of the nanowire material sample grown in the step three, and then naturally drying the solution to solidify the PMMA material, so that the nanowire array is fixed by the PMMA material;
step five: putting the nanowire array sample fixed by PMMA in the fourth step into HF acid solution, and corroding until AlxGa1-xUntil the As film sacrificial layer is completely corroded, taking out the nanowire array material fixed by PMMA, cleaning the nanowire array material by using deionized water, and waiting for the sample to be naturally air-dried after cleaning;
step six: preparing a p-type metal electrode on the upper surface of the nanowire array material fixed by PMMA (polymethyl methacrylate), and preparing an n-type electrode on the lower surface of the nanowire array material fixed by PMMA;
step seven: and (3) placing the prepared electrode and PMMA-fixed nanowire array sample into an acetone or toluene solution to be soaked for 30-60 minutes, then sequentially cleaning the nanowire array sample by using absolute ethyl alcohol and deionized water to obtain a clean sample, and naturally drying the sample to obtain the nanowire array device.
The invention has the beneficial effects that: the method firstly obtains a mobile nanowire array material fixed by PMMA material, and then the mobile nanowire array material fixed by PMMA is used for preparing the nanowire array device, so that the process difficulty of realizing the nanowire device is reduced, the technical problem existing in the preparation of a single nanowire photoelectric device is solved, the preparation of the nanowire array device is realized by the method for obtaining the nanowire array material fixed by PMMA, the nanowire array device with higher power is obtained, and the application process of the nanowire array photoelectric device is promoted.
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Fig. 1 is a schematic diagram of a method for manufacturing a nanowire array device according to the present invention.
Detailed Description
The following description of specific embodiments of the present invention is provided in connection with examples to facilitate a better understanding of the present invention.
The invention provides a preparation method of a nanowire array device, which comprises the steps of firstly obtaining a mobile nanowire array material, and growing Al on a GaAs substratexGa1-xAs thin film material As sacrificial layer, AlxGa1-xThe component of Al in As is more than or equal to 0.6 and less than or equal to 1, and the nanowire material is grown on AlxGa1-xOn the As film, after the growth of the nanowire material is finished, the nanowire material is coated on the surface of a sample in a spinning mode through PMMA material dissolved in acetone solution, standing and air-drying are carried out, then the PMMA material is solidified to fix the nanowire material, then the nanowire material sample fixed through the PMMA material is placed into HF acid corrosive liquid, and Al is etched through HF acidxGa1-xAs film material has corrosion effect, HF acid has no corrosion effect on GaAs and InAs material, and AlxGa1-xAnd the As sacrificial layer is corroded away, the GaAs and InAs materials and the solidified PMMA are not corroded by HF acid and are completely reserved, and at the moment, the mobile nanowire array material solidified by the PMMA material is obtained. Preparing a p-type metal electrode on the upper surface of a transferable nanowire array material, preparing an n-type electrode on the lower surface of the transferable nanowire array material, wherein the preparation of the n-type electrode and the p-type electrode is realized by adopting a magnetron sputtering technology, after the preparation of the n-type electrode and the p-type electrode is finished, a prepared sample is placed into an acetone or toluene solution to be soaked for 30-60 minutes, after the soaking, the sample is sequentially washed by alcohol and deionized water, and finally the sample is naturally air-dried to obtain a nanowire array device, so that the problem of obtaining a nanowire array inThe device has the difficult problem of difficult process.
The following describes in detail a method for manufacturing a nanowire array device according to the present invention with reference to the accompanying drawings and embodiments, in which the substrate is a GaAs substrate, the nanowire material is a GaAs or InAs nanowire, and the sacrificial layer material is AlxGa1-xAs thin film, AlxGa1-xThe component of Al in As is more than or equal to 0.6 and less than or equal to 1, the thickness is 5nm, and the reagent for fixing the nanowire array is PMMA material dissolved by acetone solution.
Fig. 1 is a schematic diagram of a method for manufacturing a nanowire array device according to the present invention, including: GaAs substrate 1, AlxGa1-xThe nano-wire array comprises an As thin film sacrificial layer material 2, a GaAs or InAs nano-wire material 3, a PMMA material 4 for fixing a GaAs or InAs nano-wire array, an upper surface electrode 5 of the nano-wire array material and a lower surface electrode 6 of the nano-wire array material.
The preparation method for realizing the nanowire array device provided by the embodiment is as follows:
the method comprises the following steps: cleaning the GaAs substrate, sequentially ultrasonically cleaning the GaAs substrate for 10 minutes by using acetone, absolute ethyl alcohol and deionized water, finally washing the GaAs substrate by using the deionized water and drying the GaAs substrate by using nitrogen;
step two: mixing AlxGa1-xPreparing an As film on the cleaned substrate;
step three: al grows after the second stepxGa1-xGrowing GaAs or InAs nanowires on the substrate of the As thin film sacrificial layer;
step four: dropping the solution dissolved with the PMMA material in the acetone solution on the surface of the nanowire material sample grown in the step three, and then naturally drying the solution to solidify the PMMA material, so that the nanowire array is fixed by the PMMA material;
step five: putting the GaAs or InAs nanowire array sample fixed by PMMA in the fourth step into HF acid solution, and corroding until AlxGa1-xUntil the As thin film sacrificial layer is completely corroded, taking out the GaAs or InAs nanowire array material fixed by PMMA, cleaning the GaAs or InAs nanowire array material by using deionized water, and waiting for the sample to be naturally air-dried after cleaning;
step six: preparing a p-type metal electrode on the upper surface of the GaAs nanowire array material fixed by the PMMA by adopting magnetron sputtering equipment, and preparing an n-type electrode on the lower surface of the GaAs nanowire array material fixed by the PMMA to preliminarily obtain a GaAs or InAs nanowire array device;
step seven: and (2) putting the GaAs or InAs nanowire array sample which is prepared with the electrode and is fixed by PMMA, namely the GaAs or InAs nanowire array device which is primarily realized, into an acetone or toluene solution for soaking for 30-60 minutes, then sequentially cleaning with absolute ethyl alcohol and deionized water to obtain a clean sample, and naturally drying the sample to obtain the GaAs or InAs nanowire array device which is realized by the invention.
The method for preparing the nanowire array device claimed by the application is realized through the steps, and the method is used for growing Al on PMMA materials dissolved in acetone solutionxGa1-xFixing GaAs or InAs nanowires on the As film sacrificial layer, and then utilizing HF acid solution to fix AlxGa1-xAs thin film material has corrosion effect, HF acid has no corrosion effect on GaAs material, and AlxGa1-xThe As sacrificial layer is corroded, the GaAs material and the solidified PMMA are not corroded by HF acid and are completely reserved, so that the transferable complete GaAs or InAs nanowire array material fixed by the PMMA material is obtained, the process difficulty of realizing the nanowire device is reduced, the technical problem existing in the preparation of a single nanowire photoelectric device is solved, the nanowire array device with higher power is obtained, and the application process of the nanowire array photoelectric device is promoted.
While the foregoing is directed to the preferred embodiment of the present invention, it will be understood by those skilled in the art that various changes and modifications may be made without departing from the spirit and scope of the invention.
Claims (6)
1. A method of fabricating a nanowire array device, comprising: n-type Si-doped GaAs substrate, 30-50 nm thick AlxGa1-xAs thin film sacrificial layer material, vertical GaAs or InAs nanowire array materialThe PMMA material used for fixing the vertical GaAs or InAs nanowire array material, the Ti/Au alloy metal electrode on the upper surface of the nanowire array material and the Ni/Au alloy metal electrode on the lower surface of the nanowire array material are characterized in that: the most important step of the method for preparing the nanowire array device is to obtain a transferable nanowire array material, and the implementation method of the transferable nanowire array material comprises the following specific steps: preparing Al with the thickness of 30 nm-50 nm on the surface of the substrate for growing the nano wirexGa1-xAs thin film, AlxGa1-xThe component of Al in As is more than or equal to 0.6 and less than or equal to 1, and the nanowire grows on AlxGa1-xOn an As film, spin-coating an acetone solution dissolved with a PMMA material on the surface of a prepared nanowire array material sample, obtaining a nanowire array sample fixed by PMMA after the PMMA material is cured, then putting the nanowire sample fixed by PMMA into an HF acid corrosive liquid, and using the HF acid solution to enable Al to be dissolved in the nanowire array samplexGa1-xThe method comprises the steps of removing As through corrosion, enabling an HF acid solution not to corrode a GaAs nanowire or InAs nanowire material and PMMA, completely retaining the material not corroded by the HF acid solution to obtain a migratable nanowire array material fixed by the PMMA, preparing a p-type Ti/Au alloy metal electrode on the upper surface of the migratable nanowire array material by adopting a magnetron sputtering technology, preparing an n-type Ni/Au alloy metal electrode on the lower surface of the migratable nanowire array material, finally soaking a sample with the prepared p-type electrode and n-type electrode in an acetone or toluene solution for 30-60 minutes, sequentially cleaning the sample with absolute ethyl alcohol and deionized water after the PMMA material is dissolved to obtain a clean sample, and naturally drying the sample to realize the preparation of the nanowire array device.
2. The method of claim 1, wherein the nanowires are GaAs nanowires or InAs nanowires, and the method for implementing the nanowire array device is as follows:
the method comprises the following steps: cleaning a substrate, namely cleaning the GaAs substrate for growing the GaAs or InAs nanowire by using acetone, absolute ethyl alcohol and deionized water in sequence and drying by using nitrogen;
step two: mixing AlxGa1-xPreparing an As film on the cleaned GaAs substrate;
step three: growing a nanowire material on the substrate processed in the step two;
step four: dropping the solution dissolved with the PMMA material in the acetone solution on the surface of the nanowire material sample grown in the step three, and then naturally drying the solution to solidify the PMMA material, so that the nanowire array is fixed by the PMMA material;
step five: putting the nanowire array sample fixed by PMMA in the fourth step into HF acid solution, and corroding until AlxGa1-xUntil the As film sacrificial layer is completely corroded, taking out the nanowire array material fixed by PMMA, cleaning the nanowire array material by using deionized water, and waiting for the sample to be naturally air-dried after cleaning;
step six: preparing a p-type metal electrode on the upper surface of the nanowire array material fixed by PMMA (polymethyl methacrylate), and preparing an n-type electrode on the lower surface of the nanowire array material fixed by PMMA;
step seven: and (3) placing the prepared electrode and PMMA-fixed nanowire array sample into an acetone or toluene solution to be soaked for 30-60 minutes, then sequentially cleaning the nanowire array sample by using absolute ethyl alcohol and deionized water to obtain a clean sample, and naturally drying the sample to obtain the nanowire array device.
3. The method of claim 1, wherein: the material used for fixing the nanowire array is a PMMA material dissolved in an acetone solution, the PMMA solution is coated on the surface of the nanowire sample in a spinning mode, and the fixation of PMMA on the nanowire array material is achieved after the PMMA material dissolved in the acetone solution is solidified.
4. The method of claim 1, wherein: firstly growing Al on a GaAs substrate before growing the GaAs nanowire and the InAs nanowirexGa1-xAs thin film of said AlxGa1-xThe Al component in As is more than or equal to 0.6 and less than or equal to 1.
5. The method of claim 1, wherein: after the nanowire array material is fixed by PMMA, putting the sample into HF acid solution for corrosion, wherein the HF acid solution corrodes AlxGa1-xAs, and GaAs or InAs and PMMA are not corroded by HF acid solution, so that the transferable nanowire array material is obtained.
6. The method of claim 1, wherein: preparing a p-type metal electrode on the upper surface of the transferable nanowire array material, preparing an n-type metal electrode on the lower surface of the transferable nanowire array material, then putting the device into an acetone or toluene solution to soak for 30-60 minutes to dissolve PMMA, and after the PMMA material is removed, sequentially cleaning with absolute ethyl alcohol and deionized water and naturally drying to obtain the nanowire array device.
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| TWI381536B (en) * | 2008-08-29 | 2013-01-01 | Univ Nat Taiwan | Nano or micro-structured pn junction diode arrays thin-film solar cell |
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